Pigment materials



United States Patent Ofice 2,938,873 Patented May 31, 1960 PIGMENT MATERIALS Zenon Kazenas, East Cleveland, Ohio, assignor to Switzer Brothers, Inc., Cleveland, Ohio, a corporation of Ohio No Drawing. Filed June 11, 1958, Ser. No. 741,213

25 Claims. (Cl. 252-3011) The present invention relates to new pigment materials and, more particularly, to new thermoplastic resin pigments. The invention also relates to new coating and casting compositions containing such pigments and to new methods for making such compositions.

This application is a continuation-in-part of my copending application Serial No. 673,771, filed July 24, 1957 (now abandoned), which in turn is a continuationin-part' of my copending application Serial No. 406,331, filed January 26, 1954, now US. Patent No. 2,809,954.

The new thermoplastic resin pigments of the present invention possess greatly improved light-fastness and color brightness, which permits substantially thinner films to be used to obtain optimum eifects, particularly with fluorescent dyestufis, than heretofore required. In addition, these pigments can be ground to extremely small particle sizes without loss of tinctural strength, enabling them to be used in many new applications such as in printing inks, for example, letterpress inks, gravure inks, and the like. These advantages are obtained to a more noticeable degree in daylight fluorescent pigments made in accordance with the present invention.

Although daylight fluorescent pigments have gained wide acceptance in recent years, the use of these pigments has been somewhat restricted by the lack of satisfactory light-fastness and color strength and also by the difiiculties in preparing pigments of fine particle size.

The original efforts at producing daylight fluorescent color effects simply involved attempts to dissolve dyestuffs in lacquers or shellacs. However, the use of such dye solutions or spirit varnishes proved to be completely impractical since the coatings formed had practically no light-fastness and very little, if any, daylight fluorescence.

Later, it was found that more or less satisfactory daylight fluorescent color etfects could be obtained with pigments in which daylight fluorescent dyestuifs were solvated in thermosetting resins ground to relatively coarse powder. However, these pigments were limited in lightfastness and color strength and could not be ground fine enough for many uses because of the tough, horn-like nature of the thermoset resin, loss of tinctural strength, bulking characteristics, and poor working properties when such pigments were dispersed in ink and like coating composition vehicles.

Attempts were made to use thermoplastic resins which could be ground such as, for example, acrylonitrile polymers and copolymers, polyamides, and the like, rather than thermosetting resins in the production of daylight fluorescent pigments. However, when attempts were made to grind these thermoplastic resin pigments, it was found that the pigments were often fibrous or elastic, or they softened at the temperatures encountered during grinding, or they tended to ball up and agglomerate even at temperatures below the softening point of the resins, or were too impact resistant. In addition, many of these thermoplastic resins were partially dissolved or swollen by solvents commonly employed in the paint and ink industry. Another serious shortcoming of many of these pigments was their inferior light-fastness particularly when daylight fluorescent dyes of the naphthalimide class were employed.

In view of the shortcomings of the thermosetting and, particularly, the thermoplastic resin pigments employed or attempted heretofore, it Was totally unexpected and completely surprising to find that the pigments of the present invention not only possess superior light-fastness and color strength, but, also, that they are brittle and friable below their softening point and can be easily ground at temperatures below about C. to produce the very fine particle sizes previously desired but not attainable. v

in accordance with the invention, pigments are produced by dispersing a color material, such as a dye, in a resin which is a co-condensation product of an aromatic monosulfonamide, a cyclic aminotriazine, and an aldehyde such as formaldehyde. This may be done most advantageously by any of three illustrative procedures. In two of these procedures, the colored resin is recovered in massive amorphous form and then ground to the desired particle size. In the third of these procedures, the resin particles are first formed by grinding the uncolored, solid, massive resin, and these particles are dyed by immersion in an aqueous dye bath. In all three cases, the final pigment particles are formed by the easy grinding of a substantially non-porous, massive resin, as distinguished, for example, from merely breaking up agglomerates of fine particles produced by precipitation of the resin from a liquid solution, or the diflicult grinding of a thermosetting resin which has been cured in the solid state.

By virtue of the brittle, friable character of the colored amorphous resins and the lack of porosity of the resin mass at the time of grinding, the resins inherently break down with a conchoidal fracture that is characteristic of brittle, amorphous materials, such as glass, and the resultant non-porous particles, having a minimum (or complete absence) of re-entrant surfaces, exhibit many outstanding qualities in coating compositions and particularly in printing inks. The ground pigments resist agglomeration before, during, and after dispersion in a film-forming vehicle and resist settling in many such vehicles to a remarkable degree. They have low oil absorption characteristics and do not tend to absorb or retain many solvents. They may be ground to a fine powder, or if desired, they may be initially produced, stored, and handled as relatively coarse sand-like particles up to the point of being mixed into a film-forming vehicle and then be readily broken down to the desired particle size, without balling or agglomeration, while being ground into the vehicle on a conventional 3-rol1 mill or the like.

In so far as the light-fastness of the new colored pigments is concerned, it has been found that the new pigments are better than other color pigments containing the same proportion of the same soluble dyestuffs. This characteristic makes the invention particularly applicable to pigments made with soluble fluorescent dyes, especially the rhodamines (xanthenes) and the naphthalimides.

In this connection, a film of a known sulfonamidealdehyde thermoplastic resin in which brilliant yellow 6G base had been incorporated showed a decided darkening after five hours in an Atlas Weather-ometer. On the other hand, a film of a thermoset melamine-aldehyde resin containing the same dye showed an undesirable degree of darkening after five hours in the weatherometer although the darkening was not as bad as in the case of the thermoplastic sulfonamide-aldehyde resin. However, a similar film of the new pigments of the present invention, with the same percentage of the same dye, showed substantially no darkening after five hours exposure to the same conditions in the weather-ometer.

The thermoplastic resins suitable for use in preparing thepigments and coating compositions of the present invention may be formed from an aromatic monosulfonamide having two reactive amide hydrogens, acyclic aminotriazine having 'at-least two primary amino groups and formaldehyde or paraformaldehyde.. If desired either or both of the first-mentioned components may be separately reacted with formaldehyde to form a thermoplastic sulfonamide-aldehyde resin'or a B-stage (partially condensed) v.aminotriarine-aldehyde resin, rmpectively, before'being co-condensed. The aromatic sulfonamide may comprise toluene sulfonann'de, e.g.', or p-toluene sulfonamide .or mixtures thereof, benzene .sulfonamides, orthe alkyl derivatives of such sulfonamides', and the like, in which the sulfonamidogrou'p is attached directly to' the aromatic nucleus through the sulfur atom.

Thecyclic aminotriazine compound may comprise a compound having at least two amino groups as represented by the following formula:

C-NH:

wherein R is hydrogen, alkyl (preferably less than nine carbon atoms), aryl, aralkyl, amino, and the like.

The following are typical aminotriazine compounds within the above formula: 2,4'-diamino-l,3,5-triazine 2-methyl-4,6 -diamino-1,3,5-triazine 2(3-hydroxy butyl) -4,6-diamino-l,3,5-triazine 2-hepty1-4,6-diamino-1,3,5-triazine 2-phenyl-4,6-diamino1,3,5-triazine 2-benzyl-4,6-diamino-1,3,5-triazine 2,4,6-triamino-1,3,5-triazine (melamine) In place of melamine as the'aminotriazine compound, one

, can use methyl melamine or other alkyl derivatives of melamine (i.e., N-alkyl melamines), such as the mono or dialkyl derivatives where the alkyl group may be methyl, ethyl, propyl, butyl, and the like, up to about eight carbon atoms.

Also, the B-stage methylolarninotriazine resin can be modified by forming the alkyl ether of the methylol aminotriazine. For example, this can be done by taking an A-stage methylol aminotriazine, i.e., the tri-, tetraor pentamethylol aminotriazine, and then converting to the B-stage resin in the presence ofan alkanol such as methanol, ethanol, propanol, butanol, and similar alkanols containing up to about eight carbon atoms. When using methanol, the resin would be the monoor dimethyl ether of tri-, tetraor pentamethylol aminotriazine, in partially condensed form. Also, alkanol derivatives of the aminotriazine in which the alkyl group contains more than about three carbon atoms may be formed during the course of the co-condensation reaction by introducing the the product will dilfer only slightly from the softening point of the'sulfonamide-formaldehyde resin and may not have insolubility in the desired solvents. Also, the

amount of the sulfonamide is dependent upon the number'of primary amino groups in the aminotriazine. For example, it is preferred to use about three times (on a molar basis) as much of the sulfonamide as the aminotriazine when the aminotriazine contains two amino groups, and about five times 'as much sulfonamide when the aminotriazine contains three amino groups. In other words the aminotriazine (or B-stage aldehyde-aminotriazine resin) is preferably from about 20 to 33 mol percent of the amount of monosulfonamide (or aldehydemonosulfonamide resin), although the former may be as great as about 50 mol percent and as little as about 17 mol percent of the latter.

Generally, when preparing the alkanol modified resin, it is necessary to use additional quantities of formaldehyde over and above that required for the alkanol modification so as to provide for subsequent co-condensation with the sulfonamide-formaldehyde resin. The B-stage aminotriazine-formaldehyde resin, i.e., the methylol aminotriazine, must have at least two methylol groups and preferably three such groups in order to successfully carry out the subsequent co-condesation with the sulfonamide resin.- 7

As will be noted from the following examples, the resins of the present invention may be prepared using as reactants either-formaldehyde or its polymer, paraformaldehyde, which polymer has the general formula Example 1 360 grams of mixed 0- and p-toluene sulfonamideformaldehyde resins were melted at 60-70 C. and then heated to C. At this temperature-78.4 grams of B- stage. unmodified melamine-formaldehyde resin were addedand dissolved therein. The solution .became clear at about C., and heating was continued up to C. and held there for about ten minutes. Upon cooling, the .co-condensed resin began to solidify at about 115 C. The completely condensed product (94.5% yield) was a clear water-white resin which, below about 100 C. was brittle, friable, and easily ground in amicropulverizer or by wet ball milling into a finely divided powder. a

180 grams of mixed 0- and p-toluene sulfonamideformaldehyde resins were melted at about 6070 C. and then heated up to about 130 C. 20 grams of melamine were added, and after about ten minutes the solution became clear; then 14.3 grams of paraformaldeliyde were added at 120 C. The entire mixture was then heated up from 120 C. to between 170 C. and C. while stirring over a thirty minute period. The mixturewas then clear. Upon cooling, the resulting completely condensed resin began to solidify at about 105 C. Below 100 C. the resin, which was clear and water-white, became brittle and friable, as in Example 1.

Example 3 167 grams of a mixture of oand p-toluene sulfonamide, 29.4 grams of paraformaldehyde, and 39.2 grams of the B-stage unmodifiedmelamine-formaldehyde resin were heated together to a temperature of about 170 C. for about fifteen minutes. Upon cooling, the resulting completely condensed resin began to solidify at about 115 C. The resin was clear and water-white, and below about,100C. it was brittle and friable, as in Example 1.

Example 4 168 grams of a mixture of oand p-toluene sulfonamide and 29.4 grams of paraformaldehyde were heated together to a temperature of about 170 C., while stirring, and maintained at that temperature for about twenty minutes. To this resin, at 115-120 C., were added 39 grams of the B-stage unmodified melamine-formaldehyde resin, and the mixture was heated up to 170 C. for fifteen minutes. The resulting completely condensed resin had a softening point of 115 C. and physical characteristics substantially the same as in Examples 1, 2, and 3.

Example 5 154.1 grams of a mixture of oand p-toluene sulfonamide were heated to 120 C. 20.1 grams of melamine were then added and stirred at 120 C. for fifteen minutes. 41.3 grams of paraformaldehyde were added in about seven equal portions over a period of about twenty minutes while the temperature was kept at about 1l5-120 C. After all of the paraformaldehyde was added, the temperature was raised to 170 C. for about fifteen minutes. The product resin had a softening point of about 112 C. The resin had the physical characteristics of the resins in the foregoing examples.

Example 6 To 155 grams of formalin (38% concentration) was added suflicient KOH (20% solution) to adjust the pH value of the formalin to about 9. Then 168 grams of a mixture of oand p-toluene sulfonamide were added. The mixture was heated to 100 C. and maintained at that temperature until all water had been evaporated. The temperature was then raised to 150 C. and held there for -15 minutes, during which time excess formaldehyde in the reaction mixture was distilled ofi. About 180 grams of the sulfonamide-aldehyde resin was formed. To this resin, at 115 C., was added 39 grams of the B- stage melamine-aldehyde resin, and the mixture was then heated up to 170 C. with stirring and held at that temperature for -20 minutes. The resulting completely condensed product, as in the prior examples, softened at about 115 C. and was brittle and friable below about 100 C.

Example 7 196.7 grams of a mixture of oand p-toluene sulfonamide were heated to 115 C. 36.4 grams of paraforrnaldehyde (95%) were then added slowly with mechanical stirring until thoroughly mixed. 67.8 grams of 2-phenyl-4,6-diamino-1,3,5-triazine and 31.85 grams of additional paraformaldehyde were added with stirring. When the materials were thoroughly mixed, the temperature was raised to 175-180 C. over a period of about 40 minutes and held at that temperature for an additional 10 minutes, during which time excess formaldehyde in the reaction mixture was distilled 0E. The resulting completely condensed product (87.4% yield) had the physical characteristics of the resins in the foregoing examples.

Example 8 The procedure of this example was the same as Example 7 except that 72.9 grams of 2-benzyl-4,6-dia'mino- 1,3,5-triazine were substituted for the 2-phenyl-4,6-diamino-1,3,5-triazine. The physical characteristics of the resulting completely condensed product were substantially the same as the resins of the foregoing examples.

Example 9 The procedure of this example was the same as Example 7 except that 59.5 grams of 2(beta-cyanoethy1)- 4,6-diamino-1,3,5-triazine were substituted for the 2.- phenyl-4,6-diamino-l,3,5-triazine. The resulting com pletely condensed product had the physical character istics of the resins of the foregoing examples.

Any of the foregoing clear resins can be colored to form'the pigments of the invention by introduction of the coloring material at a suitable stage up to and including production of the resin in finely-divided form.- In preparing fluorescent pigments from xanthene, naphthalimide, and/or coumarin fluorescent dyes, it is high ly desirable that the dye or dyes be completely dissolved in the resin. Additionally, the resin may be colored by other coloring materials, including other resin-sob uble dyes, organic or inorganic pigments, flatting and opacifying agents, or the like by dispersing any such coloring materials in the resin.

Examples 10 through 16 illustrate formulations for a number of dilferent dyes which may be combined with the clear resins of Examples 1 to 9 by adding the dye when the mixture has reached a temperature of be tween C. and C., while heating up to C., or by remelting the finished resin and adding the dye to the melt. The amount of dye given in each example is the amount used for each 100 grams of clear resm.

Example 10 When 1.97 grams of brilliant yellow 6G base (4 amino 1,8 naphthal 2',4' dimethyl phenylimide) and 0.22 gram of rhodamine 6 GDN Extra (Color Index No. 752) are incorporated in the resin, the final product has an orangeyellow color which is strongly daylight fluorescent when applied to surfaces by various printing methods. The dyes employed in this case are a combination of a fluorescent naphthalimide dye and a fluorescent xanthene dye.

Example 11 If 0.97 gram of rhodamine B Extra (Color Index No; 749) and 097 gram of rhodamine 6 GDN Extra are incorporated in the resin, the resulting colored resin pig-- ment is a bluish-red which is also strongly daylight fluorecent when applied to a surface as an ink. The dyes employed in this case are a combination of two xanthene dyes.

Example 12 If 3.0 grams of brilliant yellow 66 base (fluorescent naphthalimide dye) are incorporated in the resin, the resulting pigment is a lemon yellow which is also highly daylight fluorescent.

Example 13 If 0.33 gram of rhodamine B Extra and 0.5 gram of rhodamine 6 GDN Extra (two fluorescent xanthene dyes) and 1.0 gram of brilliant yellow 6G base are incorporated in the resin, the resulting pigment is a fiery-orange and is highly daylight fluorescent.

In addition to the particular fluorescent xanthene dyes used in the foregoing examples, one may use other fluorescent xanthene dyes such as, for example, xylene red (Color Index No. 748), rhodamine 56 (Color Index 746), rhodamine G (Color Index No. 750), or rhodamine 2B (Color Index No. 751).

In addition to the particular fluorescent naphthalimide dye used in the foregoing examples, one may use other fluorescent naphthalimide dyes, such as, for example:

(4 N-butyl-amino) 1,8 naphtha] n-butyl imide 4 amino 1,8 naphthal p-xenyl imide- Depending upon the particular pigment color desired, one may employ any of the fluorescent naphthalimide and fluorescent xanthene dyes, individually, or in combination with each other, or in combination with other coloring materials of the character recited above.

While the superior light-fastne'ss' of pigments made by 7 incorporating coloringmaterial in the resins herein dis-- closed is particularly pronoun'ced'when the coloring ma-' terial comprises one or moreof vthefluorescent naphthalimide and fluorescent'xanthene dyes, the invention is not so limited, and other fluorescent or non-fluorescent dyes or mixtures thereof may be used to advantage as shown in the following Examples 14, 15, and 16:

Example 14 were melted at'60-70 C. and then heated to 115 C., at which point a mixture of 37.35 grams of cadmium primrose (a non-fluorescent yellow cadmium sulfide pigment sold byI-Iarshaw Chemical Co.) dispersed in 37.35 grams of water ,was added with stirring and the heating continued. When the temperature reached 125 C., 78.4 grams of B-stage unmodified melamine-formaldehyde resin were added and dissolvedtherein. Themixture was then heated until the temperature reached 150 C., at which point 4.15 grams of rhodamine B Extra were added. Heating was continued until the temperature reached about 170 C., and then 'was held at this'temperatnre for about 10 minutes. The resulting pigment was a bright red and was highly daylight fluorescent.

Other non-fluorescent icoloring materials also may be employed in combination with the fluorescent coloring materials in the same manner that the mixture of rhodamine B Extra and cadium primrose was employed in Example 16. For example, of rutile titanium dioxide, of lithopone or 9% of chrome yellow may be dispersed in one of the fluorescent thermoplastic resin pigments of the present invention to produce difierent color efiects.

If desired, a colorless ultraviolet absorbing agent such as a nearly pure substituted'benznphenone may be added in combination with the fluorescent dyes of Examples 10- 13 and 16. The incorporation of 1% of a suitable nearly pure substituted benzophenone enhances the stability of these pigments to daylight. The addition of ultraviolet absorbing agents to daylight fluorescent pigments is the subject of Switzer et al. Patent No. 2,653,109.

In Examples 10 to 16, pigments were prepared by the preferred method of introducing the dyestufi in the molten resin. If desired, the undyed resin may be prepared in its final, solidified, finely ground state by any of the conventional grinding procedures, following which the finely ground resin may be immersed in a dye bath to incorporate one or more dyes and produce a colored'pigment. Alternatively, the solidified resin and the dye or dyes may be dissolved in a ketone or an ester solvent, the solvent.

evaporated, and the resulting colored resin then ground to pigment form; These optional procedures are illustrated in the following Examples 17 and 18:

Example 17 A dye bath was prepared as follows:

The .above materials were dissolved to'form a 0.2%.

dye bath, and 5 grams of the powdered resin of Example 1 8. were added. The dye concentration was 2% based on the weight of the resin, The dyebath and resin were warmed to' hasten incorporation of the dye in the resin, to a temperature notv above 46 C. for three minutes, andfthe dyed resin wasrthen filtered from the bath and washed with cold water until the water was substantially colorless. By comparing the color of the dyed resin and thecolor of a resin containing 1% of the same dyes which had been incorporated during manufacture as in Example 11, it was estimated that the resin powder contained 1% of the dyes.

Example i8 grams of the resin of Example. 1, before being ground, were dissolved in 300 grams of acetone along with 0.5 gram of rhodamine B Extra and 0.5 gram of rhodamine. 6. GDN Extra. .After mixing thoroughly, the acetone. was .evaporated'to leave the dyedresin in solid massive form, and the thus dyed resin was ground to pigment fineness to produce a pigment comparable to that produced in Example 17. I

The pigments prepared in the manner described in the foregoing examples are insoluble in water and aliphatic hydrocarbon solvents, are practically insoluble in aromatic hydrocarbon solvents, and are soluble in ketones and solvent esters.

Based on the physical characteristics mentioned herein, the pigments of the present invention may be used.

in a wide variety of liquid vehicle binders to form protective and decorative paints, enamels, or lacquers, silk screen inks, letterpress inks, self-sustaining resinous films, molded or extruded articles, and the like. In general, the suitable vehicle binders for obtaining the maximum benefits from the invention are those which are capable of being transformed to solid form by oxidation, solvent evaporation, or polymerization, or a combinationof such processes, and in which the pigments of the invention are substantially insoluble so that the pigments may be dispersed in the vehicle as undissolved, finelydivided particles; However, the. pigments of the invention may also be used in vehicles in which they are dissolved so that the pigmcntbecomes, in eifect, a part of the vehicle itself. Obviously, where fluorescent pigments are employed, the vehicle, should be substantially transparent, though not necessarily colorless, in order to obtain the full benefit of the fluorescent properties of the pigments. 1

. The many types of vehicle binders which may be ad vantageously colored with the pigments of'the present invention to -produce novel pigmented compositions are illustrated by the following additional-examples. In all of'these examples, the parts and percentages given are by w t- The-two following examples illustrate, respectively, an alkyd basesilkscreen ink and'a lacquer type silk screen ink, both containing the new pigment suspended in a vehicle:

* Example 19- Parts Long oil alkyd (soya type, 50% solids) 40.6 Aluminum stearate gel 8.6 Driers (metal naphthenates) 0.3 Mineral piri 6.5

Pigment as per Exampleqlo using resin of Examplel 'L; ;.....L ;...Q ;...L ;L ;...L, 44.0 The above ink, when applie clby the silk screen procuess, dries principally by oxidation to a hard film and produces a bright yellow color having a slightly orange tint;

9 Example 20 Vehicle: Parts Styrene-butadiene resin 4O Aromatic petroleum solvent having a KB. value of 70 to 90 60 To 30 parts of the above vehicle, add 4 parts of methyl dihydroabietate and 28 parts of any of the pigments of Examples 10 to 18 to produce the desired color. If desired, the resin in the above vehicle may be replaced by a mixture containing about 30 parts of cyclized rubber and 10 parts of a low molecular weight polystyrene, in which case the methyl dihydroabietate may be omitted.

The compositions of Example 20 will dry essentially by solvent evaporation to a hard colored film, and drying may be accelerated by the application of heat, if desired. Although formulated primarily as a silk screen ink, the composition may suitably be used as a coating composition for brush or spray application by adjustment of the amount of petroleum solvent to produce the desired consistency.

The following example illustrates a letterpress printing ink containing the new pigment suspended in a vehicle:

Example 21 Parts No. 3 heat bodied linseed oil 10 Pigment as per Example 14 using resin of Example 1 l Kerosene 6 Lead and manganese linoleates 3 Calcium sulfonate of mahogany acids 1 This material is dispersed on a conventional three-roll ink mill. The printing ink of this example will air dry, but, if desired, drying may be accelerated with heat in accordance with common practice in the use of printing inks.

The following example illustrates a paint containing a new pigment of the invention in combination with a conventional pigment:v

Example 22 Parts Long oil alkyd (castor oil type, 54% solids) 50- Driers (metal naphthenates) 0.7 Mineral spirits Cadmium primrose 4.5

Pigment as per Example 11 using resin of Examplel 50 Example 23 The ingredients of the following components A and B are separately mixed, as by ball milling.

Component A: Parts Chloro sulfonated polyethylene containing about 27% chlorine and 1.5% sulfur and polymerized to solid form 40 Xylol 160 Component E:

Light calcined magnesium oxide 7.4 Pigment as per Example 12 using resin of Example 1 30.0 Xylol 85.6 Mercaptobenzothiazole .8 Diphenyl guanidine .2 Hydrogenated rosin 1.0

40 parts of component A and 24.4- parts of component B are then'thoroughly mixed to produce a sprayable coating composition that sets in part by solvent evaporation and in part by vulcanization or condensation and has a pot life of about 4 hours at room temperature. Minor dilutions to adjust the viscosity for spraying may be made with xylol or toluene. The cure may be eflected at room temperature or may be accelerated by heating at temperatures up to about 110 C. for 20 to 30 minutes.

The following example is illustar'tive of a plastisol suitable for casting or molding into finished solid objects:

When this plastisol is cast or molded into bodies of appreciable thickness, it is heat cured at about 350-360 F. for long enough to reach this temperature throughout the mass which may require from 10 to 20 minutes. When formed into thin films or thin walled bodies, curing for from 3 to 5 minutes at that temperature will suflice.

The composition of this last example may be diluted by adding up to about 15 parts of V.M. & P. naphtha or 15 parts of a 50% mixture of V.M. & P. naphtha and toluol to parts of the plastisol to produce an organosol which may be more easily spread into thin films for making self-sustaining, colored, transparent sheet materials or thin Walled bodies.

Examples 19 to '24 have been given primarily to show that-the pigments of the present invention, when colored with a fluorescent naphthalimide or a fluorescent xanthene dye, are not limited in their utility to being suspended in a particular type of vehicle binder, either as regards the chemical character of the vehicle or the physical properties which render the vehicle suitable for different uses. The light-fastness, color strength, and fluorescent properties of the resultant products compared to the same vehicle compositions containing prior art pigments are imparted primarily by the new pigment resin employed in accordance with the invention as a solvent for the dye. Such improved properties are achieved to the most pronounced degree when the vehicle binder has the new pigment or pigments dispersed therein in an undissolved, finely-divided state, as illustrated by Examples 19 to 24. As should be evident from the variety of difierent vehicle binders disclosed, this improvement is independent of the chemical composition of the vehicle binder and of the process by which it is converted to a solid state, so long as the vehicle binder is not a solvent for the pigment and is substantially transparent so as to permit the fluorescent properties of pigment particles within the body of the solidified binding medium to be eflective.

The following example illustrates a coating composition in which the pigment of the invention is dissolved in the vehicle binder:

Example 25 For coating wood, the following formulation may be used:

1.1 If a sprayable composition is desired, the above formulation may be thinned out with an additional 25 grams of ethyl acetateandZS grams oftoluene. The-resulting coating istransparent and has a reddish color. :"A white or other colored primer coat may be applied to the wood before applying the resin coating so as to provide a diffusely reflecting background. 7 Such a primer cost should be used when coating a metal or the like.

Although the present invention has been described with reference to the foregoing examples,= it will be understood that variousmodifications will occur to those skilled in the art, and it is, intended that such modifications as come within the scope of the appended claims be covered thereby.

What is claimed is:

l. A process of producing a colored pigment comprising producing a thermoplastic, resinous condensation product, grinding said condensation product to finely divided form, and incorporating a coloring material in the condensation product at a stage up to and including its production in finely dividedform; said resinous condensation product being prepared by completely co-condensing, at a temperature not exceeding 180 C., a fluid reaction mass consisting essentially-of a' first component (A) selected from the class consisting of (a). a mixture of at least one aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde and at least one aromatic monosulfonarnide having two reactive amide hydrogcns, where the sulfonamido group is attached directly to the aromatic nucleus through the sulfur atom, and (b) a thermoplastic condensation product of the constituents of mixture (a), and a second component (B) selected from the class consisting of (c) a mixture of at least one aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde and at leastone aminotriazine having at least two amino groups, and (d) a therniofusible partial condensation product of the constituents of mixture the'amount of said second component (B) beingbetween about 17 and 50 mol percent ofsaid first component (A), and the totalamount of. said'aldehyde constituents being at least in excess of the total amountof said sulfonamido and'aminotriazine constituents on a molar basisL J 2. 'A process according to claim 1 in which the coloring material comprises at least oneidye selected from the class consisting of fluorescent naphthalimide dyes and fluorescent xanthene dyes, dissolved in the condensation product. 1

.3. A process according to claim 1 in which the coloring material comprises at least onedyeselected from the class consisting of fluorescent naphthalimide dyes and fluorescent xanthene dyes, incorporated by dissolving it in the condensation reaction mixture during the condensati'on step. I a

4. A process accordingto claim 1 in which'the'coloring material comprises atleast one dye selected from the class consisting of fluorescent naphthalimide dyes and fluorescent xauthene dyes, incorporated by dissolving said dye in said completely condensed thermoplastic resinous condensation product while the condensation product is'in a molten condition after its formation;

5. A process accordingto claiml in which the coloring material comprises at least one dyeselected from the class consisting of fluorescent naphthalimide dyes and fluorescent xanthene dyes,- incorporated by dissolving the completely condensed, thermoplastic,-resinous condensation product, after its formation, in a volatile solvent therefor, dissolving said dye in the resin solution, and evaporating said volatile solvent. V

6. A process according to claim 1 in which the ,aminotriazine in the resinous" condensation'pfoduct 'is meIamine.

7. A process of'pro'ducing' acolored pigment comprising producing a'th'ermoplastic, resinous condensation A productpgrinding said condensationproduct to finely divided form, dissolving a fluorescent coloring material in 12 the condensation product ata stage up to and including its production in finely divided form, and dispersing a non-fluorescent coloring material in the condensation product at a stage up to and including its production in finely divided form, said resinous condensation product being prepared by completely co-condensing, at a temperature not exceeding .180 .C., a fluid reaction mass consisting essentially of a first component (A) selected from the class consisting of (a) a mixture of at least one aldehyde entirely selected fromrthe class consisting of formaldehyde. and paraformaldehyde and at least one aromatic monosulfonamide' having two reactive amide. hydrogens, where the sulfonamido group is attached directly to the aromatic nucleus through the sulfurtatom, and (b) a thermoplastic condensation product of the constituents of mixture .(a), 1 and a second component (B) selected from the class consisting 0f.(c) t-a-mixt-ure of at least one aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde and at least one aminotriazine having at least two amino groups, and (d) a thermofusible partial condensation product of the constituents of mixture (c), the amount of said second component (B) being between about 17 and 50 mol percent of said first component (A), and the total amount of said aldehyde constituentsbeing at least in excess of the total amount of said sulfonamide and aminotriazine constituents on a molar basis. v e I e 8. A process according to claim 7 in which the nonfluorescent coloring material is a yellow pigment.

1 9. A process of producing a colored pigment comprising producinga thermoplastic, resinous condensa- (a) -a mixture of at leastone aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde and at least one aromatic monosulfonamide having'two reactive amide hydrogens, where the sulfonamido group is attached directlyto the aromatic nucleus through the sulfur atom, and (b) a thermoplastic condensation product of the constituents of mixture (a), and a second component (B) selected from the class consisting of (c) a mixture of at least one aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde and at least one aminotriazine having at least two amino groups, and (d) a thermofusible partial condensation product of the constituents of mixture (c), the amount of saidsecond component (B) being between about 17 and 5011101 percent of said first component (A), and the total amount of said aldehyde constituents being at least in excess of the total amount of said sulfonamide and aminotriazine constituents on a molar basis. a

' ponent (A) selected from the class consisting of (a) a mixture of at least one aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde and at least one toluene monosulfonamide having two reactive amide hydrogens, (b) a thermoplastic condensation product of the constituents of mixture (a), and a second component (B) selected from the class consisting of (c) a mixture of at least one aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde, and melamine, and (d) a thermofusible partial condensation product of the constituents of mixture the amount of said melamine constituent being from about 0.18 to about 0.20 mol to 1 mol of said toluene monosulfonamide constituent, and the total amount of said aldehyde constituents being at least in excess of the total amount of said sulfonamide and melamine constituents of a molar basis.

11. A process according to claim in which the coloring material comprises at least one fluorescent dye incorporated by dissolving the dye in the condensation reaction mixture during the condensation step.

12. A process according to claim 10 in which the coloring material comprises at least one fluorescent dye incorporated by dissolving the dye in said completely condensed, thermoplastic, resinous condensation product while the condensation product is in a molten condition after its formation.

13. A pigment consisting essentially of a finely divided, completely condensed, thermoplastic resin and a coloring material dispersed therein; said resin consisting essentially of the condensation product of at least one aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde, at least one aromatic monosulfonamide having two reactive amide hydrogens, where the sulfonamido group is attached directly to the aromatic nucleus through the sulfur atom, and at least one aminotriazine having at least two amino groups, the amount of said aminotriazine being between about 17 and 50 mol percent of said monosulfonamide, and the total amount of said aldehyde constituent being at least in excess of the total amount of said sulfonamide and aminotriazine constituents on a molar basis.

14. A pigment according to claim 13 in which said aminotriazine is melamine.

15. A pigment according to claim 13 in which the coloring material is a fluorescent coloring material.

16. A pigment according to claim 13 in which the coloring material comprises at least one dye selected fromthe class consisting of fluorescent naphthalimide dyes and fluorescent Xanthene dyes.

17. A pigment consisting essentially of a finely divided, completely condensed, thermoplastic resin and a coloring material dispersed therein; said resin consisting essentially of the condensation product of at least one aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde, at least one toluene monosulfonamide having two reactive amide hydrogens and melamine, the amount of said melamine being between about 17 and 20 mol percent of said monosulfonamide and the total amount of said aldehyde constituent being at least in excess of the total amount of said sulfonamide and melamine constituents on a molar basis.

18. A pigment according to claim 17 in which the coloring material is a fluorescent coloring material.

19. A pigment according to claim 17 in which the coloring material comprises at least one dye selected from the class consisting of fluorescent naphthalimide dyes and fluorescent xanthene dyes.

20. A pigment consisting essentially of a finely divided, completely condensed, thermoplastic resin, a fluorescent coloring material dissolved therein, and a non-fluorescent coloring material dispersed therein; said resin consisting essentially of the condensation product of at least one aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde, at least one aromatic monosulfonamide having two reactive amide hydrogens, where the sulfonamido group is attached directly to the aromatic nucleus through the sulfur atom, and at least one aminotriazine having at least two amino groups, the amount of said aminotriazine being between about 17 and 50 mol percent of said monosultonamide, and the total amount of said aldehyde constituent being at least in excess of the total amount of said sulfonamide and aminotriazine constituents on a molar basis.

21. A pigment according to claim 20 in which the non-fluorescent coloring material is a yellow pigment.

22. A pigmented liquid composition suitable for forming coating films and self-sustaining bodies, consisting essentially of a pigment dispersed as an undissolved, finely divided solid in a substantially transparent, liquid, vehicle binder which is not a solvent for the pigment and is convertible to a solid state, said pigment consisting essentially of a finely divided, completely condensed, thermoplastic resin and a coloring material dispersed therein; said resin consisting essentially of the condensation product of at least one aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde, at least one aromatic monosulfonamide having two reactive amide hydrogens, where the sulfonarnido group is attached directly to the aromatic nucleus through the sulfur atom, and at least one aminotriazine having at least two amino groups, the amount of said aminotriazine being between about 17 and 50 mol percent of said monosulfonamide, and the total amount of said aldehyde constituent being at least in excess of the total amount of said sulfonamide and aminotriazine constituents on a molar basis.

23. A pigmented liquid composition according to claim 22 in which the aminotriazine component of said thermoplastic resin is melamine.

24. A pigmented liquid composition suitable for forming coating films and self-sustaining bodies, consisting essentially of a pigment dispersed as an undissolved, finely divided solid in a substantially transparent, liquid, vehicle binder which is not a solvent for the pigment and is convertible to a solid state, said pigment consisting essentially of a finely divided, campletely condensed, thermoplastic resin, a fluorescent coloring material dissolved therein and a non-fluorescent coloring material dispersed therein; said resin consisting essentially of the condensation product of at least one aldehyde entirely selected from the class consisting of formaldehyde and paraformaldehyde, at least one aromatic monosulfonamide having two reactive amide hydrogens, where the sulfonarnido group is attached directly to the aromatic nucleus through the sulfur atom, and at least one aminotriazine having at least two amino groups, the amount of said aminotriazine being between about 17 and 50 mol percent of said monosulr'onamide, and the total amount of said aldehyde constituent being at least in excess of the total amount of said sulfonamide and aminotriazine constituents on a molar basis.

25. A pigmented liquid composition according to claim 24 in which the non-fluorescent coloring material is a yellow pigment.

References Cited in the tile of this patent UNITED STATES PATENTS 2,119,189 Widmer May 31, 1938 2,197,357 Widmer Apr. 16, 1940 2,498,592. Switzer Feb. 21, 1950 2,545,716 Thompson Mar. 20, 1951 2,559,976 Lindenfelser July 10, 1951 2,851,424 Switzer Sept. 9, 1958 FOREIGN PATENTS 181,405 Japan Sept. 16, 1950 505,134 Canada Aug. 17, 1954 

1. A PROCESS OF PRODUCING A COLORED PIGMENT COMPRISING PRODUCING A THERMOPLASTIC, RESINOUS CONDENSATION PRODUCT, GRINDING SAID CONDENSATION PRODUCT TO FINELY DIVIDED FROM, AND INCORPORATING A COLORING MATERIAL IN THE CONDENSATION PRODUCT AT A STAGE UP TO AND INCLUDING ITS PRODUCTION IN FINELY DIVIDED FROM, SAID RESINOUS CONDENSATION PRODUCT BEING PREPARED BY COMPLETELY CO-CONDENSING, AT A TEMPERATURE NOT EXCEEDING 180*C., A FLUID REACTION MASS CONSISTING ESSENTIALLY OF A FIRST COMPONENT (A) SELECTED FROM THE CLASS CONSISTING OF (A) A MIXTURE OF AT LEAST ONE ALDEHYDE ENTIRELY SELECTED FROM THE CLASS CONSISTING OF FORMALDEHYDE AND PARAFORMALDEHYDE AND AT LEAST ONE AROMATIC MONOSULFONAMIDE HAVING RWO REACTIVE AMIDE HYDROGENS, WHERE THE SULFONAMIDO GROUP IS ATTACHED DIRECTLY TO THE AROMATIC NUCLEUS THROUGH THE SULFUR ATOM, AND (B) A THERMOPLASTIC CONDENSATION PRODUCT OF THE CONSTITUENTS OF MIXTURE (A), AND A SECOND COMPONENT (B) SELECTED FROM THE CLASS CONSISTING OF (C) A MIXTURE OF AT LEAST ONE ALDEHYDE ENTIRELY SELECTED FROM THE CLASS CONSISTING OF FORMALDEHYDE AND PARAFORMALDEHYDE AND AT LEAST ONE AMINOTRIAZINE HAVING AT LEAST TWO AMINO GROUPS, AND (D) A THERMOFUSIBLE PARTIAL CONDENSATION PRODUCT OF THE CONSTITUENTS OF MIXTURE (C), THE AMOUNT OF SAID SECOND COMPONENT (B) BEING BETWEEN ABOUT 17 AND 50 MOL PERCENT OF SAID FIRST COMPONENT (A), AND THE TOTAL AMOUNT OF SAID ALDEHYDE CONSTITUENTS BEING AT LEAST IN EXCESS OF THE TOTAL AMOUNT OF SAID SULFONAMIDE AND AMINOTRIAZINE CONSTITUENTS ON A MOLAR BASIS. 